Synthesis and characterization of macrodiols and non-segmented poly(ester-urethanes) (PEUs) derived from α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH): effect of initiator, degree of polymerization, and diisocyanate

Nine different macrodiols derived from α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH) were prepared by ring-opening polymerization of ε-caprolactone (CL) using three linear aliphatic diols (HO–(CH2)n–OH, where n = 4, 8, and 12) as initiators and catalyzed by ammonium decamolybdate (NH4)8[Mo10O34]. The crystallization temperature (Tc) and crystallinity (xi) were relatively high for HOPCLOH species with a long aliphatic chain [–(CH2)12–] in the oligoester. Also, HOPCLOH was the precursor of twenty-seven different poly(ester-urethanes) (PEUs) with various degrees of polymerization (DP) of HOPCLOH and three types of diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), and 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI). HOPCLOH exhibited the melting temperature (Tm) and crystallinity (xi) with a proportional dependency to the degree of polymerization (DP). PEUs showed significant thermal and mechanical properties, which had a direct correlation in terms of the type of DP and diisocyanate. PEUs derived from HDI versus MDI or HMDI exhibited an apparent effect where aliphatic diisocyanate (HDI) induced a significant xi with respect to aromatic and cyclic diisocyanate (MDI or HMDI). The profile of PEUs films according to mechanical properties is mainly a plastic behavior. The chemical nature and properties of HOPCLOH and PEUs were characterized by NMR, FT-IR, GPC, MALDI-TOF, DSC, and mechanical properties.


Fig. S3 .Fig. S6 .
Fig. S3. 13 C NMR (100 MHz) spectrum in CDCl3 at room temperature for PEU4a10C.12 Fig.S4.MALDI-TOF spectrum (linear mode) expanded view for the 1000−2000 m/z fragments of HOPCL4a10OH (note: 114 and 16 are the values of the molecular weight of CL and the difference between Na + and K + (doping the same species of polymer), respectively).

Fig. S4 .
Fig. S4.MALDI-TOF spectrum (linear mode) expanded view for the 1000−2000 m/z fragments of HOPCL4a10OH (note: 114 and 16 are the values of the molecular weight of CL and the difference between Na + and K + (doping the same species of polymer), respectively).

Fig. S5 .
Fig. S5.MALDI-TOF spectrum (linear mode) expanded view for the 1000−2000 m/z fragments of HOPCL8a10OH (note: 114 and 16 are the values of the molecular weight of CL and the difference between Na + and K + (doping the same species of polymer), respectively).

Fig. S6 .
Fig. S6.Effect of number of methylenes on the crystallinity PCL for poly(esterurethanes) (PEUs) derived from poly(ε-caprolactone) diols (HOPCLOH) and 1,6hexamethylene diisocyanate (HDI).The PEUs derived from the macrodiols with DP=5 as initiator are indicated with open squares , and macrodiols are indicated with filled square ; PEUs derived from macrodiols with DP=10 as initiator are indicated with open circles , and macrodiols are indicated with filled circles , and PEUs derived from macrodiols with DP=15 as initiator are indicated with open triangles , and macrodiols are indicated with filled triangle .
a b Hard segment.c Soft segment.d Weight percent.e Obtained by DSC analysis.f g Quantified from ΔHm. h Calculated with respect to the HOPCLOH precursor.Percent determined by 1 H NMR in CDCl3.Calculated from the equation alkyl (%) = (MWinitiator/Mn(NMR)) x 100, where MWinitiator is the molecular weight of initiator or alkyl diol (HOROH).